CN106609155B - A method of producing cleaning diesel oil - Google Patents
A method of producing cleaning diesel oil Download PDFInfo
- Publication number
- CN106609155B CN106609155B CN201510705715.1A CN201510705715A CN106609155B CN 106609155 B CN106609155 B CN 106609155B CN 201510705715 A CN201510705715 A CN 201510705715A CN 106609155 B CN106609155 B CN 106609155B
- Authority
- CN
- China
- Prior art keywords
- diesel oil
- secondary processing
- oil
- fraction
- residual
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method of producing cleaning diesel oil.Secondary processing diesel oil is cut, it is divided into light secondary processing diesel oil fraction and weight secondary processing diesel oil fraction, wherein, 4 in light secondary processing diesel oil fraction, the content of 6- dimethyl Dibenzothiophene is 0~300 μ g/g, weight secondary processing diesel oil fraction is sent into residual hydrogenation reactor to react, light secondary processing diesel oil fraction and straight-run diesel oil are entered diesel oil hydrogenation reactor together to react, diesel oil hydrogenation reaction effluent is successively after separation and fractionation, gasoline fraction II and diesel oil distillate II are obtained, wherein the sulfur content of diesel oil distillate II is lower than 10 μ g/g.The present invention combines diesel oil hydrofining and residual hydrocracking, processes a large amount of secondary processing diesel oils, and production meets the diesel product of Euro V emissions under relatively mild conditions, extends the operation cycle of catalyst.
Description
Technical field
The invention belongs to obtain the method for cleaning diesel oil under conditions of there are hydrogen, more specifically, being that one kind is secondary adds
The ultra-deep hydrodesulfuration method of work diesel oil.
Background technique
Problem of environmental pollution caused by vehicle exhaust causes extensive attention in the world.Diesel oil is as important
Vehicle fuel, after burning discharge exhaust gas contained in oxysulfide (SOX), nitrogen oxides (NOX) and particulate matter (PM) etc. be
Lead to the major reason of atmosphere pollution.Diesel oil standard is increasingly strict in world wide, the low-sulfur or super-low sulfur of production environment close friend
Diesel oil has become the problem of countries in the world government and oil refining enterprise's most attention.European Union member countries came into effect Europe V from 2009
The sulfur content of diesel product is limited in 10 μ g/g or less by discharge standard, the standard.The refinery of American-European-Japanese equal countries and regions is
Through generally in the ultra-low-sulphur diesel product to market supply less than 10 μ g/g.China came into effect from 2010 is equivalent to III row of Europe
III standard of state of standard (sulfur content is less than 350 μ g/g) is put, Beijing area took the lead in carrying out the discharge for being equivalent to Europe IV in 2008
Standard is, it is specified that diesel oil sulfur content comes into effect the discharge standard for being equivalent to Europe V in 2012 less than 50 μ g/g.
But oil refining enterprise generates the secondary processing diesel oils such as a large amount of catalytic diesel oil, coker gas oil in process of production, this
The content of the dibenzothiophenes class sulfur-containing compound containing substituent group of hydrodesulfurization reaction is difficult to happen in a little secondary processing diesel oils
It is more much higher than straight-run diesel oil, and nitrogen content in secondary processing diesel oil and arene content are also much higher than straight-run diesel oil, so directly
Ultra-deep hydrodesulfuration difficulty after evaporating diesel oil incorporation secondary processing diesel oil increases considerably, and needs harsher processing item
Part.Therefore, reduce secondary processing diesel oil in the dibenzothiophenes class sulfur-containing compound containing substituent group content and nitrogen content and
Arene content can reduce the operating severity of production ultra-low-sulphur diesel process, extend catalyst life or aggrandizement apparatus processing
Amount.
CN102876374 A discloses a kind of method of inferior distillate oil hydrofinishing desulfurization, and raw material diesel oil and hydrogen are mixed
Four reaction areas is passed sequentially through after conjunction, reaction product enters separation system through cooling, obtains product liquid and hydrogen-rich gas；First
Reaction zone loads first kind catalyst, and the mixture of first kind catalyst and the second class catalyst is loaded in second reaction zone,
The second class catalyst is loaded in third reaction zone, first kind catalyst is loaded in the 4th reaction zone, and wherein the first kind is catalyzed
Agent is Mo-Co catalyst, and the second class catalyst is W-Mo-Ni catalyst or W-Ni catalyst.This method can only producing country IV mark
Quasi- diesel product.
200610196809 A1 of US, which is disclosed, a kind of diesel oil hydrofining or be hydrocracked using differential responses area
Method, this method use two reactors, high-pressure separator is added between two reactors, with remove first reactor generation
Hydrogen sulfide and the gaseous impurities such as ammonia, and then improve hydrofinishing effect, but high pressure hydrogen stripping tower is set in this method, investment
Cost and operating cost are high.
Summary of the invention
The purpose of the present invention proposes a kind of method for producing cleaning diesel oil, super to solve secondary processing diesel oil in the prior art
The problem of deep hydrodesulfurizationof method difficulty.
Method provided by the invention are as follows:
(1) secondary processing diesel oil is cut, is divided into light secondary processing diesel oil fraction and weight secondary processing diesel oil fraction,
Wherein, the content of 4,6- dimethyl Dibenzothiophene is 0~300 μ g/g in light secondary processing diesel oil fraction,
(2) that the resulting heavy secondary processing diesel oil fraction of step (1) is entered residual hydrogenation together with residual hydrogenation raw material is anti-
Device is answered, is reacted under the action of residual oil hydrocatalyst, residual hydrogenation reaction effluent successively after separation and fractionation, obtains
To gasoline fraction I, diesel oil distillate I and tail oil fraction I,
(3) light secondary processing diesel oil fraction, the resulting diesel oil distillate I of step (2) and straight-run diesel oil obtained by step (1) is together
It into diesel oil hydrogenation reactor, is reacted under the action of Hydrobon catalyst, diesel oil hydrogenation reaction effluent successively passes through
After separation and fractionation, gasoline fraction II and diesel oil distillate II are obtained, wherein the sulfur content of diesel oil distillate II is lower than 10 μ g/g.
The secondary processing diesel oil refers in addition to straight-run diesel oil, is evaporated by the diesel oil that the secondary processing process of crude oil obtains
Point, preferably the secondary processing diesel oil is catalytic cracking diesel oil and/or coker gas oil.
The present invention is by secondary processing diesel oils such as catalytic cracking diesel oil, coker gas oils according to 4,6- dimethyl Dibenzothiophene
Content is cut, and lighter secondary processing diesel oil and heavier secondary processing diesel oil are divided into, wherein heavier secondary operation bavin
Hydrotreating together in oil incorporation residual hydrogenation raw material, on the one hand can reduce the viscosity of residual oil, improve mixing for residual oil system
Property, promote the hydrogenation and removing impurity of residual oil to react, reduces residual oil hydrocatalyst coking.On the other hand residual hydrogenation equipment is utilized
The characteristics of high hydrogen partial pressure, substantially removes sulfur-bearing, nitrogenous compound and aromatic hydrocarbons in heavier secondary processing diesel oil.Residual oil adds
Hydrogen reacts resulting diesel oil distillate and enters Diesel Oil Hydrofining Unit together with lighter secondary processing diesel oil and straight-run diesel oil,
Produce ultra-low-sulphur diesel of the sulfur content less than 10 μ g/g.
The weight ratio of the heavy secondary processing diesel oil fraction into residual hydrogenation equipment and residual hydrogenation raw material is 1:19
~1:4.A certain amount of heavy secondary processing diesel oil fraction is mixed in residual hydrogenation equipment, is had little influence at residual hydrogenation equipment
Manage the ability of residual oil.
In step (1) of the present invention, secondary processing diesel oil is cut according to the content of 4,6- dimethyl Dibenzothiophene, point
For light secondary processing diesel oil and weight secondary processing diesel oil, wherein 4,6- dimethyl Dibenzothiophene in light secondary processing diesel oil
Content is 0~300 μ g/g, preferably 20~200 μ g/g, more preferably 30~100 μ g/g.
Resulting heavy secondary processing diesel oil fraction enters residual hydrogenation reactor together with residual hydrogenation raw material, in residual oil plus
It is reacted under the action of hydrogen catalyst.Reaction stream enters high pressure hot separator and is separated into gaseous stream and liquid phase stream,
Middle gaseous stream is purified, is recycled after boosting；The frequent pressure fractionating of liquid phase stream obtains gasoline fraction I, diesel oil distillate I
With tail oil fraction I.
Residual hydrogenation reactor operating condition are as follows: hydrogen partial pressure 5.0MPa~22.0MPa, 330 DEG C~450 DEG C of reaction temperature,
Volume space velocity 0.1h-1~3.0h-1, hydrogen and feedstock oil volume ratio (hydrogen-oil ratio) 350~2000.
Residual oil hydrocatalyst described in step (2) can be various existing residual oil hydrocatalysts.It is preferred that described
Residual oil hydrocatalyst is loaded catalyst, and active metal component is vib metals and/or group VIII metal, is carried
Body is aluminium oxide, silica or amorphous silica-alumina.Its more preferable active metal component be nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or
Cobalt-molybdenum, carrier are aluminium oxide.The residual hydrogenation type of reactor is fixed bed, moving bed or ebullated bed.
Light secondary processing diesel oil fraction, the resulting diesel oil distillate I of step (2) and straight-run diesel oil obtained by step (1) together into
Enter diesel oil hydrogenation reactor, is reacted under the action of Hydrobon catalyst.The diesel oil hydrogenation reactor operating condition
Are as follows: hydrogen partial pressure 3.0MPa~12.0MPa, 300 DEG C~420 DEG C of reaction temperature, volume space velocity 0.5h-1~4.0h-1, hydrogen and former
Expect the volume ratio (hydrogen-oil ratio) 150~1000 of oil.
The Hydrobon catalyst is loaded catalyst, and active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum
Or cobalt-molybdenum, carrier are one or more of aluminium oxide, silica, amorphous silica-alumina.It can be various existing diesel oil to add
Hydrogen catalyst for refining.
The diesel oil hydrogenation type of reactor can be gas-liquid-solid three-phase fixed-bed, be also possible to gas-liquid two-phase fixed bed.
The present invention has the advantages that
1, the present invention combines diesel oil hydrofining and residual hydrocracking, processes a large amount of secondary processing diesel oils,
Compared with the diesel product that production under conditions of mitigation meets Euro V emissions, extend the operation cycle of catalyst.
2, weight secondary processing diesel oil fraction is mixed in residual oil especially decompression residuum, and residual hydrogenation dress can be greatly lowered
Feedstock viscosity is set, the diffusivity and removing impurities qualitative response rate of reactant is improved, can inhibit residual hydrogenation reactor rear portion bed
Carbon deposit, extend the residual hydrogenation equipment operation cycle.
Detailed description of the invention
Fig. 1 is the method schematic diagram of production cleaning diesel oil provided by the invention.
Fig. 2 is the process flow diagram that comparative example 1 and comparative example 2 use.
Fig. 3 is the process flow diagram that comparative example 1 ' and comparative example 2 ' use.
Specific embodiment
Attached drawing is the method schematic diagram of production cleaning diesel oil provided by the invention, and many equipment are omitted in figure, such as pumps, change
Hot device, compressor etc..Method of the invention is further described below by attached drawing, but does not therefore limit this hair
It is bright.
As shown in Figure 1, the residual oil raw material from pipeline 13, the heavy secondary processing diesel oil fraction from pipeline 14 with from pipe
Line 15, pipeline 22 hydrogen mixing after enter residual hydrogenation reactor 16, reacted under the action of residual oil hydrocatalyst；
Reaction product enters high pressure hot separator 18, isolated liquid product and gas-phase product through pipeline 17, and wherein gas-phase product passes through
Pipeline 20 carries out further gas-liquid separation, isolated liquid product and gas-phase product into cold high pressure separator 21.Cold height
The gas-phase product of separator is pressed to remove H2After S through pipeline 22 enter circulating hydrogen compressor, after boosting with the new hydrogen from pipeline 15
It is mixed after mixing with feedstock oil.The liquid product of high pressure hot separator 18 and the liquid product of cold high pressure separator 21 are respectively through pipe
Line 19 and pipeline 23 enter fractionating column 24, and fractionation obtains gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I, wherein gas
Body, gasoline fraction I and tail oil fraction I go out device through pipeline 25,26 and 27 respectively；Diesel oil distillate I enters diesel oil hydrogenation through pipeline 3
Reactor 5.
The diesel oil distillate I of the light secondary processing diesel oil fraction of straight-run diesel oil, pipeline 2 from pipeline 1 and pipeline 3 with come from
Pipeline 4, pipeline 9 hydrogen mixing after enter diesel oil hydrogenation reactor 5, reacted under the action of Hydrobon catalyst,
Diesel oil hydrogenation reaction effluent enters cold high pressure separator 7, isolated liquid product and gas-phase product through pipeline 6；Gas phase produces
Object removes H2Enter circulating hydrogen compressor through pipeline 9 after S, is mixed after being mixed after boosting with the new hydrogen from pipeline 4 with feedstock oil.
Liquid product enters fractionating column 10 through pipeline 8, obtains gas, gasoline fraction II and diesel oil distillate II after being fractionated, wherein gas
It is separated through pipeline 12 into downstream unit with gasoline fraction II, diesel oil distillate II goes out device through pipeline 11.
The following examples will be further described the present invention, but be not intended to limit the present invention.
Straight-run diesel oil raw material A used in the examples, secondary processing diesel oil B and C, residual oil D, property are shown in Table 1, secondary operation
Light secondary processing diesel oil fraction B 1, C1 and weight secondary processing diesel oil fraction B 2, C2 is respectively cut into diesel oil, wherein 4,6- bis- in B1
The content of methyldibenzothiophene is that the content of 4,6- dimethyl Dibenzothiophene in 95 μ g/g, C1 is 175 μ g/g.
Hydrogenation protecting agent that diesel hydrogenation test uses, Hydrobon catalyst is by Sinopec catalyst branch Chang Ling
Catalyst plant production, trade names are respectively RG-1, RS-2000, and admission space ratio is 1:10.Residual hydrogenation test uses
Hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst are by Sinopec catalyst branch Chang Ling catalyst plant
Production, trade names are respectively RG-30A, RDM-32, RMS-30, and admission space ratio is 5:45:50.
Table 1
Embodiment 1
The diesel oil distillate I of straight-run diesel oil A, light secondary processing diesel oil fraction B 1 and residual hydrogenation cellular manufacture are mixed with hydrogen
It is latter same into diesel oil hydrogenation unit, deep hydrodesulfurizationof reaction, reaction condition are carried out under the action of Hydrobon catalyst
Are as follows: 345 DEG C of reaction temperature, volume space velocity 1.5h when raw material oil liquid-1, hydrogen partial pressure 6.4MPa, hydrogen-oil ratio 500.Reactor outflow
Object passes through isolated diesel oil distillate II, and product property is shown in Table 2.
Residual oil raw material D, weight secondary processing diesel oil fraction B 2 mixed with hydrogen it is latter with enter residual hydrogenation reactor, in slag
It is reacted under the action of oil hydrogenation catalysts, reaction condition is 395 DEG C of reaction temperature, volume space velocity when raw material oil liquid
0.237h-1, hydrogen partial pressure 17.0MPa, hydrogen-oil ratio 600.Reactor effluent passes through isolated gas, gasoline fraction I, diesel oil
Fraction I and tail oil fraction I, major product property are shown in Table 2.Diesel oil distillate I goes diesel oil hydrogenation reactor to be reacted.
Comparative example 1
Comparative example 1 uses straight-run diesel oil A, secondary processing diesel oil B for raw material, and process flow is as shown in Figure 2.From pipeline 1
Straight-run diesel oil A, pipeline 2 secondary processing diesel oil B mixed with the hydrogen from pipeline 3 and pipeline 8 after enter diesel oil hydrogenation it is anti-
Device 4 is answered, is reacted under the action of Hydrobon catalyst；Reaction product enters cold high pressure separator 6, separation through pipeline 5
Obtain liquid product and gas-phase product；Gas-phase product removes H2After S through pipeline 8 enter circulating hydrogen compressor, after boosting with come from
It is mixed after the new hydrogen mixing of pipeline 3 with feedstock oil.The liquid product of cold high pressure separator 6 enters fractionating column 9, separation through pipeline 7
Gas, gasoline fraction II and diesel oil distillate II are obtained, wherein gas and gasoline fraction II enter downstream unit through pipeline 11 and separate,
Diesel oil distillate II goes out device by pipeline 10.
Residual oil raw material from pipeline 12 is reacted with after the mixing of the hydrogen of pipeline 13 and pipeline 20 into residual hydrogenation
Device 14 is reacted under the action of residual oil hydrocatalyst；Reaction product enters high pressure hot separator 16, separation through pipeline 15
Liquid product and gas-phase product are obtained, wherein gas-phase product enters cold high pressure separator 19 through pipeline 18, and isolated liquid phase produces
Object and gas-phase product.The gas-phase product of cold high pressure separator 19 removes H2Enter circulating hydrogen compressor through pipeline 20 after S, after boosting
It is mixed after being mixed with the new hydrogen from pipeline 13 with feedstock oil.The liquid product and cold high pressure separator 19 of high pressure hot separator 16
Liquid product enter fractionating column 22 through pipeline 17 and pipeline 21 respectively, isolated gas, gasoline fraction I, diesel oil distillate I and
Tail oil fraction I, wherein gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I go out to fill through pipeline 23,24,25 and 26 respectively
It sets.Reaction condition and major product property are shown in Table 2.
Comparative example 1 '
The diesel oil that comparative example 1 uses straight-run diesel oil A, secondary processing diesel oil B and residual hydrogenation equipment to produce is raw material, technique
Process is as shown in Figure 3.The secondary processing diesel oil B and the hydrogen from pipeline 3 and pipeline 8 of straight-run diesel oil A, pipeline 2 from pipeline 1
Enter diesel oil hydrogenation reactor 4 after gas mixing, is reacted under the action of Hydrobon catalyst；Reaction product is through pipeline 5
Into cold high pressure separator 6, isolated liquid product and gas-phase product；Gas-phase product removes H2Enter after S through pipeline 8 and recycles
Hydrogen compressor mixes after mixing after boosting with the new hydrogen from pipeline 3 with feedstock oil.The liquid product of cold high pressure separator 6 passes through
Pipeline 7 enters fractionating column 9, and isolated gas, gasoline fraction II and diesel oil distillate II, wherein gas and gasoline fraction II are through pipe
Line 11 enters downstream unit and separates, and diesel oil distillate II goes out device by pipeline 10.
Residual oil raw material from pipeline 12 is reacted with after the mixing of the hydrogen of pipeline 13 and pipeline 20 into residual hydrogenation
Device 14 is reacted under the action of residual oil hydrocatalyst；Reaction product enters high pressure hot separator 16, separation through pipeline 15
Liquid product and gas-phase product are obtained, wherein gas-phase product enters cold high pressure separator 19 through pipeline 18, and isolated liquid phase produces
Object and gas-phase product.The gas-phase product of cold high pressure separator 19 removes H2Enter circulating hydrogen compressor through pipeline 20 after S, after boosting
It is mixed after being mixed with the new hydrogen from pipeline 13 with feedstock oil.The liquid product and cold high pressure separator 19 of high pressure hot separator 16
Liquid product enter fractionating column 22 through pipeline 17 and pipeline 21 respectively, isolated gas, gasoline fraction I, diesel oil distillate I and
Tail oil fraction I, wherein gas, gasoline fraction I and tail oil fraction I go out device through pipeline 23,24,26 respectively, and diesel oil distillate I is through pipe
Line 25 enters diesel oil hydrogenation reactor 4.Reaction condition and major product property are shown in Table 2.
Table 2
| Process conditions | Embodiment 1 | Comparative example 1 | Comparative example 1 ' |
| Diesel oil hydrogenation unit | |||
| Diesel oil unit processing capacity (relative to embodiment 1) | 1 | 0.899 | 0.975 |
| Raw material composition, weight | |||
| Straight-run diesel oil A, % | 36.0 | 40.0 | 36.9 |
| Secondary processing diesel oil B, % | - | 60.0 | 55.4 |
| Light secondary processing diesel oil fraction B 1, % | 37.8 | - | - |
| Diesel oil distillate I, % | 26.2 | - | 7.7 |
| Process conditions | |||
| Reactor such as entrance hydrogen partial pressure, MPa | 6.4 | 6.4 | 6.4 |
| Reactor average reaction temperature, DEG C | 345 | 372 | 375 |
| Volume space velocity when reactor liquid, h-1 | 1.50 | 1.39 | 1.50 |
| Hydrogen to oil volume ratio under standard state | 500 | 500 | 500 |
| Diesel oil distillate II main character | |||
| Sulfur content, μ g/g | 8 | 8 | 8 |
| Residual hydrogenation unit | |||
| Raw material composition, weight | |||
| Residual oil D, % | 81.6 | 100 | 100 |
| Weight secondary processing diesel oil fraction B 2, % | 18.4 | - | - |
| Process conditions | |||
| Reactor such as entrance hydrogen partial pressure, MPa | 17.0 | 17.0 | 17.0 |
| Reactor average reaction temperature, DEG C | 395 | 395 | 395 |
| Volume space velocity when reactor liquid, h-1 | 0.248 | 0.20 | 0.20 |
| Hydrogen to oil volume ratio under standard state | 600 | 600 | 600 |
| Generate oily main character | |||
| Sulfur nutrient, % | 0.5 | 0.8 | 0.8 |
| Carbon residue mass fraction, % | 6.5 | 8.4 | 8.4 |
| Nickel content, μ g/g | 5 | 9 | 9 |
| Content of vanadium, μ g/g | 8 | 11 | 11 |
| Product quality distribution, % | |||
| Gas+gasoline fraction I | 9.2 | 8.6 | 8.6 |
| Diesel oil distillate I | 29.8 | 10.5 | 10.5 |
| Tail oil fraction I | 61.0 | 80.9 | 80.9 |
The total amount phase of straight-run diesel oil A, secondary processing diesel oil B and residual oil D that embodiment 1, comparative example 1 and comparative example 1 ' are processed
Together.
Secondary processing diesel oil B is that 95 μ g/g are cut according to the content of 4,6- dimethyl Dibenzothiophene by embodiment 1,
The content of 4,6- dimethyl Dibenzothiophene is 95 μ g/g in light secondary processing diesel oil fraction B 1, and remaining part is attached most importance to secondary add
Work diesel oil distillate B2.Wherein diesel oil hydrogenation unit processes straight-run diesel oil A, light secondary processing diesel oil fraction B 1 and comes from residual hydrogenation
The diesel oil distillate I of unit, total diesel oil processing capacity are denoted as 100%, and diesel oil hydrogenation unit can give birth under 345 DEG C of mean temperature
Diesel oil distillate II of the output sulfur content less than 10 μ g/g.Residual hydrogenation unit process residual oils D and weight secondary processing diesel oil fraction B 2,
Therefore air speed is higher, has reached 0.248h-1, but due to the incorporation of weight secondary processing diesel oil fraction B 2, charging is greatly lowered
Viscosity not only improves the diffusivity and removing impurities qualitative response rate of reactant, and the content for generating well cuts is lower, and can press down
The carbon deposit of residual hydrogenation reactor processed rear portion bed extends the residual hydrogenation equipment operation cycle.
1 diesel oil hydrogenation unit of comparative example processing straight-run diesel oil A and secondary processing diesel oil B, total diesel oil processing capacity are only
89.9%, and diesel oil unit needs just produce diesel oil of the sulfur content less than 10 μ g/g under 372 DEG C of mean temperature and produces
Product.Residual hydrogenation unit process residual oils D, although air speed only has 0.2h-1, but since resid feed viscosity is high, diffusivity is weak,
The content for not only generating well cuts is higher, but also the carbon deposit of hydrogenator rear portion bed is serious, influences residual hydrogenation equipment
Operation cycle.
1 ' diesel oil hydrogenation unit of comparative example processing straight-run diesel oil A, secondary processing diesel oil B and diesel oil distillate I, total diesel oil add
Work amount is 97.5%, but diesel oil hydrogenation unit needs can just produce sulfur content less than 10 μ g/ under 375 DEG C of mean temperature
The diesel product of g.Residual hydrogenation unit process residual oils D, although air speed only has 0.2h-1, but since resid feed viscosity is high, expand
The ability of dissipating is weak, and the content for not only generating well cuts is higher, but also the carbon deposit of residual hydrogenation reactor rear portion bed is serious, influences
The residual hydrogenation equipment operation cycle.
In conclusion not only diesel oil processing capacity is big using the solution of the present invention, diesel oil hydrogenation cell-average reaction temperature
Low, Hydrobon catalyst service life is long, in addition, the content of the generation well cuts of residual oil unit is lower.
Embodiment 2
The diesel oil distillate I of straight-run diesel oil A, light secondary processing diesel oil fraction C1 and residual hydrogenation cellular manufacture are mixed with hydrogen
It is latter same into diesel oil hydrogenation unit, deep hydrodesulfurizationof reaction, reaction condition are carried out under the action of Hydrobon catalyst
Are as follows: 353 DEG C of reaction temperature, volume space velocity 1.5h when raw material oil liquid-1, hydrogen partial pressure 6.4MPa, hydrogen-oil ratio 500.Reactor outflow
Object passes through isolated diesel oil distillate II, and product property is shown in Table 2.
Residual oil D, weight secondary processing diesel oil fraction C2 mix with hydrogen it is latter together into residual hydrogenation reactor, in residual oil plus
It is reacted under the action of hydrogen catalyst, reaction condition is 395 DEG C of reaction temperature, body speed 0.23h when raw material oil liquid-1, hydrogen partial pressure
For 17.0MPa, hydrogen-oil ratio 600.Reactor effluent is evaporated by isolated gas, gasoline fraction I, diesel oil distillate I and tail oil
Divide I, major product property is shown in Table 2.Diesel oil distillate I enters diesel oil hydrogenation unit and carries out hydrofining reaction.
Comparative example 2
Comparative example 1 uses straight-run diesel oil A, secondary processing diesel oil C for raw material, and process flow is as shown in Figure 2.Reaction condition and
Major product property is shown in Table 3.
Comparative example 2 '
The diesel oil that comparative example 1 uses straight-run diesel oil A, secondary processing diesel oil C and residual hydrogenation equipment to produce is raw material, technique
Process is as shown in Figure 3.Reaction condition and major product property are shown in Table 3.
Table 3
| Process conditions | Embodiment 2 | Comparative example 2 | Comparative example 2 ' |
| Diesel oil hydrogenation unit | |||
| Diesel oil unit processing capacity (relative to embodiment 1) | 1 | 0.902 | 0.977 |
| Raw material composition, weight | |||
| Straight-run diesel oil A, % | 36.1 | 40.0 | 36.9 |
| Secondary processing diesel oil C, % | 60.0 | 55.4 | |
| Light secondary processing diesel oil fraction C1, % | 43.3 | ||
| Diesel oil distillate I, % | 20.6 | 7.7 | |
| Process conditions | |||
| Reactor such as entrance hydrogen partial pressure, MPa | 6.4 | 6.4 | 6.4 |
| Reactor average reaction temperature, DEG C | 353 | 375 | 377 |
| Volume space velocity when reactor liquid, h-1 | 1.50 | 1.39 | 1.50 |
| Hydrogen to oil volume ratio under standard state | 500 | 500 | 500 |
| Diesel oil distillate II main character | |||
| Sulfur content, μ g/g | 8 | 8 | 8 |
| Residual hydrogenation unit | |||
| Raw material composition, weight | |||
| Residual oil D, % | 87.0 | 100 | 100 |
| Weight secondary processing diesel oil fraction C2, % | 13.0 | - | - |
| Process conditions | |||
| Reactor such as entrance hydrogen partial pressure, MPa | 17.0 | 17.0 | 17.0 |
| Reactor average reaction temperature, DEG C | 395 | 395 | 395 |
| Volume space velocity when reactor liquid, h-1 | 0.23 | 0.20 | 0.20 |
| Hydrogen to oil volume ratio under standard state | 600 | 600 | 600 |
| Generate oily main character |
| Sulfur nutrient, % | 0.6 | 0.8 | 0.8 |
| Carbon residue mass fraction, % | 6.9 | 8.4 | 8.4 |
| Nickel content, μ g/g | 6 | 9 | 9 |
| Content of vanadium, μ g/g | 9 | 11 | 11 |
| Product quality distribution, % | |||
| Gas+gasoline fraction I | 9.0 | 8.6 | 8.6 |
| Diesel oil distillate I | 24.9 | 10.5 | 10.5 |
| Tail oil fraction I | 66.1 | 80.9 | 80.9 |
The total amount phase of straight-run diesel oil A, secondary processing diesel oil C and residual oil D that embodiment 2, comparative example 2 and comparative example 2 ' are processed
Together.
Secondary processing diesel oil C is that 175 μ g/g are cut according to the content of 4,6- dimethyl Dibenzothiophene by embodiment 2
It cuts, the content of 4,6- dimethyl Dibenzothiophene is 175 μ g/g in light secondary processing diesel oil fraction C1, and remaining part attaches most importance to two
Secondary processing diesel oil distillate C2.Wherein diesel oil hydrogenation unit processes straight-run diesel oil A, light secondary processing diesel oil fraction C1 and comes from residual oil
The diesel oil distillate I of hydrogenation unit, total diesel oil processing capacity are denoted as 100%, and diesel oil hydrogenation unit can be in 353 DEG C of mean temperature
Under produce diesel oil distillate II of the sulfur content less than 10 μ g/g.Residual hydrogenation unit process residual oils D and weight secondary processing diesel oil evaporate
Divide C2, therefore air speed is higher, has reached 0.23h-1, but due to the incorporation of weight secondary processing diesel oil fraction C2, be greatly lowered
Feedstock viscosity not only improves the diffusivity and removing impurities qualitative response rate of reactant, and the content for generating well cuts is lower, and
It can inhibit the carbon deposit of residual hydrogenation reactor rear portion bed, extend the residual hydrogenation equipment operation cycle.
1 diesel oil hydrogenation unit of comparative example processing straight-run diesel oil A and secondary processing diesel oil C, total diesel oil processing capacity are only
90.2%, and diesel oil hydrogenation unit needs can just produce bavin of the sulfur content less than 10 μ g/g under 375 DEG C of mean temperature
Oil product.Residual hydrogenation unit process residual oils D, although air speed only has 0.2h-1, but since resid feed viscosity is high, diffusion energy
Power is weak, and the content for not only generating well cuts is higher, but also the carbon deposit of residual hydrogenation reactor rear portion bed is serious, influences residual oil
The hydrogenation plant operation cycle.
The diesel oil of 1 ' diesel oil hydrogenation unit of comparative example processing straight-run diesel oil A, secondary processing diesel oil C and residual hydrogenation equipment evaporates
Divide I, total diesel oil processing capacity is 97.7%, but diesel oil unit needs can just produce sulphur under 377 DEG C of mean temperature and contain
Measure the diesel product less than 10 μ g/g.Residual hydrogenation unit process residual oils D, although air speed only has 0.2h-1, but due to residual oil into
Expect that viscosity is high, diffusivity is weak, and the content for not only generating well cuts is higher, but also the product of residual hydrogenation reactor rear portion bed
Charcoal is serious, influences the residual hydrogenation equipment operation cycle.
In conclusion not only diesel oil processing capacity is big using offer scheme of the invention, diesel oil hydrogenation cell-average reaction temperature
Spend low, Hydrobon catalyst service life is long, in addition, the content of the generation well cuts of residual hydrogenation unit is lower.
Claims (10)
1. a kind of method for producing cleaning diesel oil, comprising:
(1) secondary processing diesel oil is cut, is divided into light secondary processing diesel oil fraction and weight secondary processing diesel oil fraction,
In, the content of 4,6- dimethyl Dibenzothiophene is 0 ~ 300 μ g/g, the secondary processing diesel oil in light secondary processing diesel oil fraction
Refer in addition to straight-run diesel oil, the diesel oil distillate obtained by the secondary processing process of crude oil,
(2) the resulting heavy secondary processing diesel oil fraction of step (1) is entered into residual hydrogenation reactor together with residual hydrogenation raw material,
It is reacted under the action of residual oil hydrocatalyst, residual hydrogenation reaction effluent successively after separation and fractionation, obtains vapour
Oil distillate I, diesel oil distillate I and tail oil fraction I,
(3) light secondary processing diesel oil fraction, the resulting diesel oil distillate I of step (2) and straight-run diesel oil obtained by step (1) enter together
Diesel oil hydrogenation reactor is reacted under the action of Hydrobon catalyst, and diesel oil hydrogenation reaction effluent is successively through separating
After fractionation, gasoline fraction II and diesel oil distillate II are obtained, wherein the sulfur content of diesel oil distillate II is lower than 10 μ g/g.
2. the method according to claim 1, wherein the secondary processing diesel oil be catalytic cracking diesel oil and/
Or coker gas oil.
3. the method according to claim 1, wherein 4,6- dimethyl two in the light secondary processing diesel oil fraction
The content of benzothiophene is 20 ~ 200 μ g/g.
4. the method according to claim 1, wherein 4,6- dimethyl two in the light secondary processing diesel oil fraction
The content of benzothiophene is 30 ~ 100 μ g/g.
5. the method according to claim 1, wherein residual hydrogenation reactor operating condition are as follows: hydrogen partial pressure
5.0MPa~22.0MPa, 330 DEG C~450 DEG C of reaction temperature, volume space velocity 0.1h-1~3.0h-1, hydrogen and feedstock oil volume
Than 350~2000.
6. the method according to claim 1, wherein the residual oil hydrocatalyst be loaded catalyst,
Active metal component is vib metals and/or group VIII metal, and carrier is aluminium oxide, silica or amorphous silica-alumina.
7. the method according to claim 1, wherein the residual hydrogenation type of reactor is fixed bed, movement
Bed or ebullated bed.
8. the method according to claim 1, wherein diesel oil hydrogenation reactor operating condition are as follows: hydrogen partial pressure
3.0MPa~12.0MPa, 300 DEG C~420 DEG C of reaction temperature, volume space velocity 0.5h-1~4.0h-1, hydrogen and feedstock oil volume
Than 150~1000.
9. the method according to claim 1, wherein Hydrobon catalyst is loaded catalyst, activity
Metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and carrier is aluminium oxide, silica, one in amorphous silica-alumina
Kind is several.
10. the method according to claim 1, wherein the diesel oil hydrogenation type of reactor is gas-liquid-solid three-phase
Fixed bed or gas-liquid two-phase fixed bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510705715.1A CN106609155B (en) | 2015-10-27 | 2015-10-27 | A method of producing cleaning diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510705715.1A CN106609155B (en) | 2015-10-27 | 2015-10-27 | A method of producing cleaning diesel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106609155A CN106609155A (en) | 2017-05-03 |
| CN106609155B true CN106609155B (en) | 2019-03-22 |
Family
ID=58615288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510705715.1A Active CN106609155B (en) | 2015-10-27 | 2015-10-27 | A method of producing cleaning diesel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106609155B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1212374C (en) * | 2001-07-31 | 2005-07-27 | 中国石油化工股份有限公司 | Method for reducing aromatic content of diesel oil in residual hydrogenation equipment |
| CN101311252B (en) * | 2007-05-24 | 2012-07-18 | 中国石油化工股份有限公司 | Process for producing ultralow sulfur diesel fuels |
| CN102344828B (en) * | 2010-08-05 | 2014-05-28 | 中国石油化工股份有限公司 | Processing method of inferior residual oil |
| CN104593068B (en) * | 2013-10-31 | 2017-03-22 | 中国石油化工股份有限公司 | A method of producing gasoline with a high octane number from residual oil |
| CN104593069B (en) * | 2013-10-31 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of residual hydrocracking and catalytic cracking combined processing method |
-
2015
- 2015-10-27 CN CN201510705715.1A patent/CN106609155B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106609155A (en) | 2017-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100587038C (en) | Hydrogenation method for producing good quality catalytic cracking material | |
| CN100510023C (en) | Production of cleaning fuel from heavy-fraction oil | |
| CN100577773C (en) | Gas oil and residual oil hydrotreating process for producing catalytically cracked material | |
| CN101348732A (en) | Heavy distillate oil hydrotreating method | |
| CN102899081B (en) | Wax oil hydrotreating method | |
| CN101747936B (en) | Hydrogenation method for producing high-quality low-sulfur diesel fraction | |
| CN103773495A (en) | Hydrotreatment-catalytic cracking combination process method | |
| CN103805247A (en) | Combination method used for processing inferior diesel oil | |
| CN103525461A (en) | Hydrocracking method | |
| CN102344826B (en) | Combined hydrogenation method for producing catalytic raw material and high-quality diesel oil | |
| CN100419044C (en) | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil | |
| CN102465011A (en) | Hydrotreatment method of heavy distillate oil | |
| CN103059967B (en) | Mixed hydrogenation method for catalytic cracking gasoline and coking diesel oil | |
| CN106609155B (en) | A method of producing cleaning diesel oil | |
| CN106520197B (en) | A kind of method for hydrogen cracking that boat coal is produced by inferior feedstock oil | |
| CN102719272B (en) | A kind of catalysis conversion method of petroleum hydrocarbon | |
| CN102465027A (en) | Hydrotreating method of heavy distillate oil | |
| CN102911730B (en) | Catalytic conversion method for high sulfur wax oil | |
| CN102719274B (en) | High efficiency catalytic conversion method of petroleum hydrocarbon | |
| CN102453536B (en) | Integrated hydrogenation method for producing clean diesel | |
| CN103059993B (en) | Catalytic conversion method of petroleum hydrocarbon | |
| CN105441127A (en) | Method for producing jet fuel | |
| CN106520191B (en) | It is a kind of to strengthen the method for hydrogen cracking for adding hydrogen | |
| CN106520195B (en) | A kind of method for hydrogen cracking for improving boat coal quality | |
| CN104611036B (en) | A kind of height does heavy distillate oil hydrotreating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |